Kinetics of the Gas−Liquid Reaction between Carbon Dioxide and Hydroxide Ions

Kucka, L.; Kenig, Eugeny Y.; Górak, Andrzej

doi:10.1021/ie020452f

Cited by 89 publications

(72 citation statements)

References 12 publications

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“…1) with a plane, horizontal gas-liquid interface was used for the absorption studies [24]. The main advantage of the stirred cell is that the rates of absorption can be measured using a liquid with a single, known composition.…”

Section: Methodsmentioning

confidence: 99%

A Study on CO₂ Absorption Kinetics by Aqueous Solutions of N,N‐Diethylethanolamine and N‐Ethylethanolamine

Vaidya

Kenig

2009

Chem Eng & Technol

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N-Ethylethanolamine (EEA) and N,N-diethylethanolamine (DEEA) represent promising candidate alkanolamines for CO 2 removal from gaseous streams, as they can be prepared from renewable resources. In this work, the reaction rate constant for the reaction between CO 2 and EEA was determined from the absorption rate measurements of CO 2 in a blend comprising DEEA, EEA and H 2 O. A stirred-cell reactor with a plane, horizontal gas-liquid interface was used for the absorption studies. While the DEEA concentration in the formulated solution was varied in the range of 1.5-2.5 kmol/m 3 , the initial EEA concentration was 0.1 kmol/m 3 . A zwitterion mechanism for EEA and a base-catalyzed hydration mechanism for DEEA were used to describe the reaction kinetics. At 303 K, the second-order reaction rate constant for the CO 2 reaction with EEA was found to be 8041 m 3 /(kmol s). The liquid-side mass transfer coefficient was also estimated, and its value (0.004 cm/s) is in line with those typical of stirred-cell reactors.

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Section: Methodsmentioning

confidence: 99%

A Study on CO₂ Absorption Kinetics by Aqueous Solutions of N,N‐Diethylethanolamine and N‐Ethylethanolamine

Vaidya

Kenig

2009

Chem Eng & Technol

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“…(14)) and the diffusivity of carbon dioxide in water as given by Danckwerts (1970). The use of the Stokes-Einstein relationship is generally accepted in this form to calculate the diffusion coefficient of carbon dioxide in hydroxide solutions (Nijsing et al, 1959;Kucka et al, 2002).…”

Section: Physical Properties Employed In the Interpretation Of The Flmentioning

confidence: 99%

“…In these studies it has been found that the reaction rate constant is not only dependent on the concentrations of the reacting species, but also affected by the ionic strength of the caustic solution and the nature of the cations present in the hydroxide solution (Nijsing et al, 1959;Pohorecki and Moniuk, 1988;Kucka et al, 2002). The following two reactions are generally accepted to take place:…”

Section: Introductionmentioning

confidence: 99%

“…In literature, the kinetics of reaction 1 are typically described using an irreversible-secondorder reaction rate expression (r = k OH − c CO 2 c OH − ), where all possible effects of non-idealities are lumped in the reaction rate constant k OH − (Pohorecki and Moniuk, 1988;Kucka et al, 2002). This approach is generally sufficient to represent the experimental data of a single specific study but lacks the fundamental character of the reaction rate constant only being a function of temperature.…”

Section: Introductionmentioning

confidence: 99%

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The applicability of activities in kinetic expressions: A more fundamental approach to represent the kinetics of the system CO2–OH
Haubrock
¹
,
Hogendoorn
²
,
Versteeg
³

2007
Chemical Engineering Science
42
0
25
0
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The applicability of utilizing activities instead of concentrations in kinetic expressions has been investigated using the reaction of CO 2 in sodium hydroxide solutions also containing different neutral salts (LiCl, KCl and NaCl) as model system. For hydroxide systems it is known that when the reaction rate constant is based on the use of concentrations in the kinetic expression, this "constant" depends both on the counterion in the solution and the ionic strength which is probably caused by the strong non-ideal behavior of various components in the solution. In this study absorption rate experiments have been carried out in the pseudo-first-order absorption rate regime. The experiments have been interpreted using a new activity based kinetic rate expression instead of the traditional concentration-based rate expression.A series of CO 2 absorption experiments in different NaOH (1, 1.5, 2.0 mol l −1 )-salt (LiCl, NaCl or KCl)-water mixtures has been carried out, using salt concentrations of 0.5 and 1.5 mol l −1 all at a temperature of 298 K. Interpretation of the data additionally required the use of an appropriate equilibrium model (needed for the calculation of the activity coefficients), for which, in this case, the Pitzer model was used. The additions of the salts proved to have a major effect on the observed absorption rate. The experiments were evaluated with the traditional concentration based-approach and the "new" approach utilizing activity coefficients. With the traditional approach, there is a significant influence of the counter-ion and the hydroxide concentration on the reaction rate. The evaluation of the experiments with the "new" approach-i.e. incorporating activity coefficients in the reaction rate expressions-reduced the influence of the counter-ion and the hydroxide concentration on the reaction rate constant considerably. The absolute value of the activity based-reaction rate constant k m OH − ( ) for sodium hydroxide solutions containing either LiCl, KCl or NaCl is in the range between 10 000 and 15 000 kg (kmol −1 s −1 ) compared to the traditional approach where the value of the lumped reaction rate constant k OH − is between 7000 and 34 000 m 3 (kmol −1 s −1 ).Therefore, it can be concluded that the application of the new methodology is thought to be very beneficial especially in processes where "the thermodynamics meet the kinetics". Based on this it is anticipated that the new kinetic approach will first find its major application in the modeling of integrated processes like Reactive Distillation, Reactive Absorption and Reactive Extraction processes where both, thermodynamics and kinetics, are of essential importance and, additionally, activity coefficients deviate substantially from unity. ᭧

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“…This technique has been widely applied to determine reaction rate constants involved in chlorine hydrolysis, H 2 S absorption in chlorine solution, flue desulfurization, NOx absorption or CO 2 capture in amine solutions. [5][6][7][8][9][10][11][12][13][14][15][16] Most of time, reactive absorption is applied using (i) batch reactors in which the gas and liquid phases are separated by a flat interface (stirred-cell reactor). The absorption rate, and consecutively the reaction rate, are deduced 4 pressure at the contactor outlet was nearly identical to the inlet one, and only the reactant concentration decay over time was recorded to determine the mass-transfer and chemical reaction rates.…”

Section: Introductionmentioning

confidence: 99%

Assessment of a Stirred-Cell Reactor Operated Semicontinuously for the Kinetic Study of Fast Direct Ozonation Reactions by Reactive Absorption

Dang

Biard

Couvert

2016

Ind. Eng. Chem. Res.

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A jacketed stirred-cell reactor, operated semi-continuously, was used to assess the kinetics of fast ozonation reactions by reactive absorption. The method was applied to the direct ozone reaction with resorcinol. A high resorcinol concentration was used to reach a steady state and to neglect the byproducts accumulation. Thus, the mass-transfer rate, and consecutively the reaction rate, were deduced from the ozone mass balance in the gas phase. The gas-phase and liquid-phase mass-transfer coefficients were previously measured directly through the ozone absorption in appropriated conditions. The results emphasized the high sensitivity of the reaction rate constant to the ozone physicochemical properties, especially its solubility, which is controversial in the literature. Therefore, several correlations used to calculate the ozone solubility in water were considered to calculate the second-order reaction rate constant, which varied from 3.57-4.68 10 5 L mol -1 s -1 at 20°C to 9.50-12.2 10 5 L mol -1 s -1 at 35°C. The activation energy was in the range 35-59 kJ mol -1 depending on the considered ozone solubility correlation. A sensitivity analysis is provided to assess the influence of the experimental conditions and ozone physicochemical properties on the model. Finally, the applicability of this method is thoroughly discussed.2

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Kinetics of the Gas−Liquid Reaction between Carbon Dioxide and Hydroxide Ions

Cited by 89 publications

References 12 publications

A Study on CO₂ Absorption Kinetics by Aqueous Solutions of N,N‐Diethylethanolamine and N‐Ethylethanolamine

A Study on CO₂ Absorption Kinetics by Aqueous Solutions of N,N‐Diethylethanolamine and N‐Ethylethanolamine

The applicability of activities in kinetic expressions: A more fundamental approach to represent the kinetics of the system CO2–OH
Haubrock
¹
,
Hogendoorn
²
,
Versteeg
³

2007
Chemical Engineering Science
42
0
25
0
View full text Add to dashboard Cite

Assessment of a Stirred-Cell Reactor Operated Semicontinuously for the Kinetic Study of Fast Direct Ozonation Reactions by Reactive Absorption

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Kinetics of the Gas−Liquid Reaction between Carbon Dioxide and Hydroxide Ions

Cited by 89 publications

References 12 publications

A Study on CO2 Absorption Kinetics by Aqueous Solutions of N,N‐Diethylethanolamine and N‐Ethylethanolamine

A Study on CO2 Absorption Kinetics by Aqueous Solutions of N,N‐Diethylethanolamine and N‐Ethylethanolamine

The applicability of activities in kinetic expressions: A more fundamental approach to represent the kinetics of the system CO2–OHHaubrock1, Hogendoorn2, Versteeg3 2007Chemical Engineering Science420250View full textAdd to dashboardCite

Assessment of a Stirred-Cell Reactor Operated Semicontinuously for the Kinetic Study of Fast Direct Ozonation Reactions by Reactive Absorption

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A Study on CO₂ Absorption Kinetics by Aqueous Solutions of N,N‐Diethylethanolamine and N‐Ethylethanolamine

A Study on CO₂ Absorption Kinetics by Aqueous Solutions of N,N‐Diethylethanolamine and N‐Ethylethanolamine

The applicability of activities in kinetic expressions: A more fundamental approach to represent the kinetics of the system CO2–OH
Haubrock
¹
,
Hogendoorn
²
,
Versteeg
³

2007
Chemical Engineering Science
42
0
25
0
View full text Add to dashboard Cite